Amino and amido dialkyl tin carboxylates

ABSTRACT

Amino and amido dialkyltin dicarboxylates and stannoxy carboxylates are prepared by first reacting an amine or amino alcohol with a dicarboxylic acid anhydride, followed by reaction of the resulting product with a dialkyltin oxide. The obtained compounds are useful as catalysts for promoting reaction of organic isocyanates with organic compounds having one or more active hydrogen-containing groups.

The present invention relates to catalyzing the reaction between organic isocyanates with organic compounds containing an active hydrogen group and is particularly concerned with the preparation of stable organo tin catalysts of high activity for use in production of polyurethanes.

BACKGROUND OF PRIOR ART

A wide variety of tin carboxylate compounds have been proposed for use as catalysts in the preparation of polyurethanes. Certain of these are in commercial use, either alone or as co-catalysts with tertiary amine catalysts. U.S. Pat. No. 3,164,557, proposes certain organotin compounds containing a tertiary nitrogen atom for use as polyurethane catalysts. The compounds in said patent correspond to the general formula ##STR1## wherein R₁ and R₂ are hydrocarbon radicals and X₁ and X₂ are stated to be organic radicals, at least one of which contains a tertiary nitrogen atom. Typical of the tin compounds thus proposed is ##STR2##

The use of organotin compounds containing tertiary nitrogen is also disclosed in British Patent No. 899,948. The compounds therein disclosed are either unstable amino alkoxides containing a ##STR3## group (prepared from an alkanolamine and a tin oxide) or amino carbonates having a tin nitrogen bond. The tin nitrogen bond is much less stable than that in tin carboxylates.

Organo-substituted tin amino-carbamates, which are proposed for use as catalysts in preparation of polyurethane foams according to U.S. Pat. No. 3,796,674, also contain a tin nitrogen bond. The polyurethane foam catalysts disclosed in U.S. Pat. Nos. 3,681,271 and 3,703,484 are stannoxane type compounds, prepared by reacting a diallkyltin oxide with an acid or acid derivative. According to the earlier of these patents, the presence of a ##STR4## bond boosts the catalytic activity.

BRIEF SUMMARY OF THE INVENTION

It has now been found, in accordance with the present invention, that organotin compounds of unexpectedly high catalytic activity and good stability are had, when such compounds contain one or more functional groups from among ##STR5## as obtained, for example, by reaction of a tin oxide with an amido acid or an amino acid ester of the types: ##STR6##

The compounds produced in accordance with the invention correspond respectively to either of the generic formulas ##STR7## wherein R₁ and R₂ are independently H, alkyl groups of 1 to 20 carbon atoms; hydroxyalkyl or alkoxyalkyl of 2 to 20 carbon atoms; or R₁ and R₂, together form a heterocyclic ring of 5 or 6 atoms; ##STR8## in which n=zero or one and R₆ is hydrogen or an alkyl or an alkyl hydrocarbyl group of up to 20 carbon atoms;

A and B are carbon atoms linked by a single or double bond or together comprise part of six membered ring from the group consisting of cyclohexane, cyclohexene and benzene;

R₄ and R₅ are independently alkyl groups of 1 to 20 carbon atoms, phenyl, or cyclo alkyl groups of 6 to 20 carbon atoms.

The invention includes these novel compounds as such and methods for their preparation, as well as methods and compositions for the use of these organotin compounds as catalysts, alone or in combination with other catalysts, for isocyanate reaction with active hydrogen containing compounds, such as in the preparation of polyurethanes.

DETAILED DESCRIPTION OF THE INVENTION

The compounds of the present invention can be prepared in two steps. In the first step, an amine or an amino alcohol is reacted with an acid anhydride, respectively in accordance with the following equations: ##STR9##

In the next step the compound produced in equation III or that in equation IV above, respectively, is reacted with a dialkyltin oxide, thus: ##STR10##

By reacting only one mole of the amido or amino compound per mole of dialkyltin oxide, the compounds obtained correspond respectively to that shown in equations VII and VIII below:

The following examples illustrate preparation of the novel compounds of the invention.

EXAMPLE 1

Into a 1 liter 3-neck, round bottom flask was charged 100 gs (1 mole) of succinic anhydride and 400-500 cc of toluene. The flask was then equipped with a mechanical stirrer and a reflux condenser mounted on a Dean-Stark trap and an addition funnel. The flask was heated with stirring to 120° C. When the succinic anhydride was completely dissolved, 89 gs (1 mole) of dimethylethanolamine (DMEA) were added slowly. After the addition of the amine was completed, the reaction mixture was cooled to 70° C. and 125 gs (1/2 mole) of dibutyl-tin oxide were added and the reaction mixture reheated to the refluxing point of toluene and the azeotroped water collected in the Dean-Stark trap. A total of 12 gs of water was collected after 4 hours. The reaction was cooled again to room temperature and the toluene removed on a rotovac. The viscous pale residue weighed 301.4 gs. It was analyzed by infrared and nuclear magnetic resonance spectroscopy. The composition of this product was: ##STR12## 11.3 mole % succinic acid 27.8 mole % toluene

EXAMPLES 2 and 3

The same apparatus was used as in Example 1. The materials charged were 1 mole of tetrahydrophthalic anhydride and 300 cc of toluene. The toluene was gently heated to reflux until all the anhydride was dissolved; then 1 mole of dialkylalkanol amine (either diethylethanol amine or DMEA) was added from an addition funnel slowly over a period of about 1 hour. The reaction mixture was then cooled to about 50° C. and 1/2 mole of dibutyltin oxide was added rapidly. The reaction mixture was then refluxed again and the water formed azeotroped out into the Dean-Stark trap. When the theoretical amount of water 1/2 mole (9 cc) was removed, the reaction mixture was transferred to a rotovac where the toluene was removed under reduced pressure. The residue was weighed and analyzed by infrared and nuclear magnetic resonance spectroscopy. The infrared spectra showed ester carbonyl bands at 1725 cm⁻¹. It also showed the total absence of --OH and anhydride carbonyl bands, indicating the complete reaction of alkanolamine with the anhydride and dibutyltin oxide and suggesting the following structure: ##STR13## This structure was further confirmed by NMR and elemental analysis as shown in Table I below:

                  TABLE I                                                          ______________________________________                                         Amine       Elemental Analysis                                                                              Refractive                                        Example                                                                               Used     Calculated                                                                               Found    Index at 25° C.                      ______________________________________                                         2      diethyl- C      56.17                                                                               56.22    1.5150                                           ethanol- H      8.08  8.16                                                     amine    N      3.45  3.45                                                              Sn     15.4 14.65 ± .17                                     3      dimethyl-                                                                               C      53.71                                                                               52.61    1.5073                                           ethanol- H      7.83  7.64                                                     amine    N      3.92  3.15                                                              Sn     16.64                                                                               17.02 ± 0.03                                    ______________________________________                                    

EXAMPLE 4

The apparatus and procedure used were the same as in Examples 2 and 3 except the amine was dibutyl amine and the resulting product had the amido structure. ##STR14## The infrared analysis shows the absence of OH and anhydride carbonyl, and the nuclear magnetic resonance spectra shows 86 mole % of structure XI and 14 mole % toluene in the crude product. The refractive index at 22° C. is 1.5076. Elemental analysis on a purified sample was as follows: Calculated for Molecule XI--C--60.53%, H--8.82%, N--3.53%, Sn--15.00%, Found--C--60.74%, H--8.95%, N--3.27%, Sn--15.15±0.05.

EXAMPLE 5

The same procedure and apparatus were employed in this example as those of Example 4, except the amine was N,N-bis-hydroxyethylamine (commonly known as diethanolamine). Diglyme (124 g per 105 g DEA) was also used as co-solvent with toluene. At the end of the reaction and after the theoretical amount of water was azeotroped out, the reaction mixture was cooled to room temperature. The product separated out as a gummy bottom layer. Yield=38.8% of theoretical. This product was analyzed for structure XII. ##STR15##

Calculated for structure XII: C--51.54, H--7.24, N--3.76, Sn--15.97 Found: C--56.22, H--8.16, N--3.45, Sn--15.3±0.12

EXAMPLE 6

Using an apparatus similar to the one described in Example 1, 309.4 gs (2 moles) of cyclohexane dicarboxylic acid anhydride was reacted with 259.8 gs (2 moles) of dibutyl amine in 422.8 gs of toluene. The resulting amido carboxylic acid was then reacted in situ with 498.0 gs (2 moles) of dibutyltin oxide. Total reaction time was 4 hours. The amount of water removed was 18.5 cc (1 mole). The weight of the product recovered was 1026.0 g and % recovery 97.8. The IR of the product shows the absence of any NH or OH bands, and it shows the characteristic amid and carboxylate carbonyl absorptions. This coupled with the amount of water obtained suggests the stannoxy carboxylate structure XIII Refractive index at 25° C. was 1.5112. ##STR16## The nuclear magnetic resonance analysis also supports the above structure. It shows the methylene on nitrogen proton at 3.2 ppm with an area/H=0.77. It also shows the rest of the protons at 0.7-2.0 ppm with an area/H=0.77.

EXAMPLES 7-11

The same procedure was used as Examples 2-4 except that the molar ratio of the amine to anhydride to dibutyltin oxide was changed to 1:1:1. In this method 1/2 mole of water was obtained per 1 mole of dibutyltin oxide and the products obtained have the general structure: ##STR17## Table II below lists the various amines used in this preparation.

                  TABLE II                                                         ______________________________________                                                               Refrac-                                                  Ex-                   tive     Elemental Analysis                              am-                   Index    in Wt. %                                        ple  Amine     Anhydride  @ 25° C.                                                                       (Calc'd)                                                                              (Found)                                ______________________________________                                         7    DMEA      Tetrahydro-                                                                               1.5175 C   49.90                                                                               50.02                                               phthalic          H   7.48  7.57                                                                 N   2.91  2.33                                                                 Sn  24.74                                                                               25.3                                                                           ± 0.04                            8    Diethyl-  Tetrahydro-                                                                               1.4869                                                    ethanol   phthalic                                                             amine                                                                     9    Dimethyl- Tetrahydro-                                                                               1.4865                                                    amino     phthalic                                                             propanol                                                                  10   B--hy-    Tetrahydro-                                                                               22° C.                                             droxy-    phthalic   1.5244                                                    ethyl                                                                          morpholine                                                                11   Dimethyl  Tetrahydro-                                                                               22° C.                                                                         C   50.91                                                                               50.65                                     isopropanol                                                                              phthalic   1.5180 H   7.68  7.43                                     amine                       N   2.83  1.52                                                                 Sn  24.04                                                                               24.74                                ______________________________________                                          The infrared spectra of these compounds also show the absence of OH and      anhydride bands and show the ester carbonyl bands at ˜1725-1730      cm.sup.-1. Nuclear magnetic resonance analysis also confirms the above      structure (XIV). An example of NMR analysis is shown in Table III.

                  TABLE III                                                        ______________________________________                                         NMR analysis for structure (Example 10)                                         ##STR18##                                                                     Type of                                                                        Protons  Chemical Shift                                                                              No. of Protons                                                                             Area/H                                       ______________________________________                                         X        4.5-3.5       6          3.5                                          Y        3.5-2.2      12          4.3                                          Z        2.2-0.6      18          4.3                                          W        5.7           2          2.5*                                         ______________________________________                                          Total Count 159 for 38 protons which is 4.2/proton.                            *While this integration figure is less than it should be, the operator         believes it is due to a problem in the instrument.                       

EXAMPLE 12

The procedure employed in this example was the same as in examples 6-10 except that the amine was dimethyl ethanol amine. The product obtained has the structure of type (XV). ##STR19## Infrared analysis shows the expected ester carbonyl bands at 1725-1730 cm⁻ and the absence of the OH and anhydride carbonyl band. The nuclear magnetic resonance analysis shows the expected chemical shift for all the protons of the above molecules. The NMR analysis also shows toluene contaminants.

EXAMPLE 13

Following the same procedure as in Example 11, dimethylethanol amine, cyclohexane, 1,2-dicarboxylic acid-anhydride and dibutyltin oxide were reacted in 1:1:1/2 molar ratios respectively. One mole of water per mole of tin oxide was obtained. The product was analyzed by IR and NMR spectroscopy and confirmed to be of structure (XVI). Further confirmation was obtained from elemental analysis. The analysis in wt. % for Molecule XVI was: Calculated: C--53.56, H--8.09, N--3.91, Sn--16.59; Found: C--32.92, H--8.29, N--3.53, Sn--15.94±0.12. ##STR20##

The compounds of the present invention were found to be useful as catalysts for isocyanate alcohol and isocyanate water reaction. In general, these compounds are effective catalysts for the reaction of isocyanate with active hydrogen containing compounds. They are superior in catalytic activity and hydrolytic stability to standard catalysts such as dibutyltin dilaurate used in the preparation of urethane polymers. The following examples demonstrate the effectiveness and other advantages of these compounds in catalyzing urethane polymer forming reactions.

EXAMPLE 14

In this example a flexible foam formulation was chosen to evaluate the catalysts of the present invention. The "one shot" hand mix technique was used in the preparation of foams. The composition of this formulation is shown below.

    ______________________________________                                         Formulation 1                                                                         Components                                                                               pbw                                                           ______________________________________                                         (1)      Voranol 3010                                                                               173.0                                                              Water       7.8                                                       (2)      Silicone L-6202                                                                            2.7                                                       (3)      Hylene ™ 90.0                                                               Catalysts   as shown in                                                                    Table IV                                                  ______________________________________                                    

                                      TABLE IV                                     __________________________________________________________________________     Catalysts Used and Their Activities in                                         Formulation 1                                                                  Catalyst   pbw/184 gr Resin                                                    __________________________________________________________________________     (4)                                                                              DABCO 33-LV                                                                             0.5                                                                 (5)                                                                              T-9      0.3                                                                   Example 6    0.75                                                              Example 13         0.75                                                        Example 12             0.38                                                    Example 10                  0.75                                               Example 7                       0.38                                         Reactivity                                                                     Cream Time 13  16    16  16   16  16                                           (secs.)                                                                        Hard Gel Time                                                                             85/87                                                                              100/105                                                                              80/85                                                                              85/90                                                                               80/85                                                                              84/86                                        (secs.)                                                                        Rise time (secs.)                                                                         75  90    78  80   72  76                                           Physical Properties                                                            Density lbs/cu ft                                                                         1.3 1.29  1.27                                                                               1.27 1.29                                                                               1.25                                         Air flow cu ft/min                                                                        5.35                                                                               4.70  1.31                                                                               4.0  3.15                                                                               1.53                                         Number of cells/                                                                          54.5                                                                               53.0  55.0                                                                               55.0 62.0                                                                               56                                           inch                                                                           Tear lbs/inch                                                                             2.76                                                                               2.15  2.74                                                                               2.07 2.25                                                                               2.31                                         % Elongation                                                                              207 99    215 151  125 174                                          __________________________________________________________________________      (1) Voranal 3010 is a triol of 3000 M. Wt; hydroxy no. 54.4-58.4; markete      by Dow Chemical Company.                                                       (2) Silicone L6202 is a surfactant marketed by Union Carbide.                  (3) Hylene ™ is DuPont's trade name for toluene diisocyanate.               (4) DABCO 33LV is trademark for triethylenediamine; marketed by Air            Products.                                                                      (5) T9 is stannous octoate; marketed by M & T.                           

It can be seen from the above example that good flexible foams can be made by the catalysts of the present invention at considerably lower concentration than the control. Also, it is important to note that flexible foams were made by these catalysts alone and without the addition of the usually expensive amine co-catalyst. In certain urethane formulations tertiary amine catalysts are best employed together with organotin compounds. The tin compounds of the invention may be similarly used in such co-catalyst systems, often with advantages over the previously employed tin compounds, as will hereinafter appear.

EXAMPLE 15

The compounds of the invention were evaluated in rigid foam formulation 2 by the "one shot" hand mix technique. The reactivity of the catalysts was compared to standard rigid urethane catalysts and is shown in Table V.

The data of Tables V and VI show that the compounds of the present invention are as good catalysts for preparing rigid urethane foams as standard commercial catalysts.

EXAMPLE 16

The compounds of the present invention were evaluated in yet another rigid foam formulation using the "one shot" method and by hand mix techniques. The formulation used was that of 3, and the reactivity and physical properties obtained on these foams are shown in Tables VII and VIII.

Again, the data demonstrate the effectiveness of these compounds in the preparation of rigid urethane foams.

                                      TABLE V                                      __________________________________________________________________________     RIGID FOAM DATA                                                                __________________________________________________________________________             1   2   3   4   5   6   7   8                                          __________________________________________________________________________     Temp., °C.                                                                      31  31  31  31  31  32  32  32                                         Polycat 8                                                                              .8  --  --  --  --  --  --  --                                         Rigid Foam                                                                             157.5                                                                              157.5                                                                              157.5                                                                              157.5                                                      157.5   157.5                                                                              157.5                                                                              157.5                                                          Premix (g)                                                                     50% (Ex 13)                                                                            --  .5  .3  .1  .2  --  --  --                                         50% (Ex 12)                 .3  .15 .10                                        50% (Ex 10)                                                                    75% (Ex 7)                                                                     25% Diglyme                                                                    50% T-1                                                                        D.P.G.                                                                         50% (Ex 6)                                                                     50% T-12                                                                       D.P.G.                                                                         Hylene TIC (g)                                                                         105 105 105 105 105 105 105 105                                        Initial 13  13  13  15  14  13  14  15                                         Strings 47/50                                                                              35/40                                                                              35  50  40  30/35                                                                              40  50                                         Tack Free                                                                              65  40/45                                                                              45  80  60  40  55/60                                                                              75                                         Rise    115 90  90  120 115 85  90  110                                        __________________________________________________________________________             9   10  11  12  13  14  15  16                                         __________________________________________________________________________     Temp., °C.                                                                      32  32  32  32  32  32  32  32                                         Polycat 8                                                                              --  --  --  --  --  --  --  .8                                         Rigid Foam                                                                     Premix (g)                                                                             157.5                                                                              157.5                                                                              157.5                                                                              157.5                                                                              157.5                                                                              157.5                                                                              157.5                                                                              157.5                                      50% (Ex 13)                                                                            --  --  --  --  --  --  --  --                                         50% (Ex 12)                                                                            --  --  --  --  --  --  --  --                                         50% (Ex 10)                                                                            .15 --  --  --  --  --  --  --                                         75% (Ex 7)  .15 --  --  --  --  .10 --                                         25% Diglyme                                                                    50% T-1                                                                        D.P.G.          1.5 .10 --  --  --  --                                         50% (Ex 6)              .15 --  --  --                                         50% T-12                                                                       D.P.G.                      .10 --  --                                         Hylene TIC (g)                                                                         105 105 105 105 105 105 105 105                                        Initial 15  14  14  15  15  15  15  13                                         Strings 45  35  40  40  50  50  45  47/50                                      Tack Free                                                                              65  50  55  65  80/85                                                                              85  80  65                                         Rise    105 100 100 105 110 115 115 113/115                                    __________________________________________________________________________

                                      TABLE VI                                     __________________________________________________________________________     Physical Properties on Hand Mixed Rigid Foams Made                             with Amino and Amidotin Carboxylates                                                            Formulation 2                                                                              pbw                                                              (6)                                                                              Selectrofoam 6406                                                                          109                                                              (7)                                                                              DC-193      1.5                                                              (8)                                                                              Freon 11B   47                                                                 Catalyst    As Shown                                                         (9)                                                                              Hylene TIC  105                                               Catalyst    Concentration, pbw                                                 __________________________________________________________________________     (10) Polycat 8                                                                             0.8                                                                Example 13      0.1                                                            Example 12          0.1                                                        Example 10              0.15                                                   Example 6                   0.15                                               Example 7                       0.1                                            (11) T-12                           0.1                                        Density, lbs/cu. ft.                                                                       1.41                                                                               1.44                                                                               1.40                                                                               1.42                                                                               1.44                                                                               1.41                                                                               1.42                                       Cell Count/Inch                                                                            65  65  50  65  75  85  90                                         Dimensional Stability                                                          at 158° F. @ 100% R.H.                                                              13.6                                                                               10.0                                                                               8.4 9.0 9.0 8.6 10.5                                       After 7 Days                                                                   Oxygen Index                                                                               19  19  19  19  19  19  19                                         Initial K-Factor                                                                           0.155                                                                              0.153                                                                              0.156                                                                              0.152                                                                              0.153                                                                              0.153                                                                              0.146                                      K-Factor, Aged 1 Week                                                                      0.195                                                                              0.194                                                                              0.200                                                                              0.188                                                                              0.194                                                                              0.194                                                                              0.189                                      at 158° F. @ 100% R.H.                                                  __________________________________________________________________________      (6) Selectrofoam 6406 is a high functionality polyol derived from sucrose      and amine; marketed by PPG.                                                    (7) DC 193 is a silicone surfactant; marketed by Dow Corning.                  (8) Freon 11B is chlorofluoromethane; marketed by DuPont.                      (9) Hylene TIC is crude TDI; marketed by DuPont.                               (10) Polycat 8 is the trademark of Abbott for dimethylcyclohexylamine.         (11) T12 is the trademark of M & T for dibutyltin dilaurate.                   (12) Mondur MR is the trademark of Mobay Chemical for polyisocyanate;          functionality of 2.6, eq. wt. 131.                                       

                                      TABLE VII                                    __________________________________________________________________________     RIGID FOAM DATA                                                                __________________________________________________________________________                    1   2    3   4   5   6   7   8                                  __________________________________________________________________________     Temp., °C.                                                                             28  28   28  28  28  28  29  29                                 33-LV 0.75                                                                     .82            .82 --   --  --  --  --  --  --                                 T-10.07                                                                        Polycat 8                                                                             1.5                                                                                 1.57                                                                              --  1.57 --  --  --  --  --  --                                 T-1    0.07                                                                    Rigid Foam Mix (g)                                                                            157.5                                                                              157.5                                                                               157.5                                                                              157.5                                                                              157.5                                                                              157.5                                                                              157.5                                                                              157.5                              50% (Ex 13)    --  --   .5  --  --  --  --  --                                 50% (Ex 12)                         .5  .75 --                                 50% (Ex 10)                                 .5                                 75% (Ex 7)                                                                     50% T-1                     .5  --  --  --  --                                 50% T-12                        .5  --  --  --                                 .sup.(12) Mondur MR (g)                                                                       100 100  100 100 100 100 100 100                                Initial        42  41   32  30  39  47  40  45                                 Strings        85  70   60  55  70  80  65/70                                                                              75/80                              Tack Free      105 85   85  70  105 100 80  105                                Rise           115 105/110                                                                             105 90  115 110 105 130                                __________________________________________________________________________                    9   10   11  12  13  14  15  16                                 __________________________________________________________________________     Temp., C.      29  30   30  30  31  31  31  31                                 Polycat 8                                                                             1.5                                                                                 1.57                                                                              --  --   --  --    --                                                                               --  --  1.57                               T-1    0.07                                                                    Rigid Foam Mix (g)                                                                            157.5                                                                              157.5                                                                               157.5                                                                              157.5                                                                              157.5                                                                              157.5                                                                              157.5                                                                              157.5                              50% (Ex 13)    --  --   --  --   -- --  --  --                                 50% (Ex 12)    --  --   --  --  --  --  --  --                                 50% (Ex 10)    .75 --   --  --  --  --  --  --                                 75% (Ex 7)         .5   --  --  --  --  --  --                                 50% (Ex 6)              .5  .75 1.0 1.0*                                                                               .75*                                                                               --                                 .sup.(12) Mondur MR (g)                                                                       100 100  100 100 100 100 100 100                                Initial        38  37   48  45  37  37  45  37                                 Strings        70  68   85  75  65  60/65                                                                              75  65                                 Tack Free      85/90                                                                              75/80                                                                               110 95  80  75/78                                                                              95  75/80                              Rise           105 100  135 125 105 95/100                                                                             120 105                                __________________________________________________________________________      *50% dioctyl phthalate                                                   

                                      TABLE VIII                                   __________________________________________________________________________     Physical Properties on Hand Mixed Rigid Foams Made with Amino and              Amidotin                                                                       Carboxylates                                                                   __________________________________________________________________________             Formulation 3    pbw                                                           Voranol 370     111                                                            Fluorocarbon 11SBA                                                                             46                                                             DC-193          1.5                                                            Catalyst        As Shown                                                       Mondur MR       100                                                    Catalyst    Concentration, pbw                                                 __________________________________________________________________________     DABCO 33-LV 0.75                                                               T-1         0.07                                                               Polycat 8       1.5                                                            T-1             0.07                                                           50% T-12 in DOP     0.5                                                        50% Example 12          0.75                                                   50% Example 10              0.75                                               50% Example 7                   0.75                                           50% Example 6                       1.0                                        Density, lbs/cu. ft.                                                                       1.92                                                                               1.96                                                                               1.94                                                                               1.90                                                                               1.96                                                                               1.90                                                                               1.94                                       Oxygen Index                                                                               20  20  20  20  20  20  20                                         Dimensional Stability                                                          at 158° F. @ 100% R.H.                                                  1 Day, % Vol. Change                                                                       5.5 6.6 6.0 7.0 7.07                                                                               6.94                                                                               6.44                                       7 Days, % Vol. Change                                                                      9.9 10.72                                                                              10.10                                                                              10.6                                                                               11.5                                                                               9.98                                                                               9.86                                       Initial K-Factor                                                                           0.155                                                                              0.158                                                                              0.166                                                                              0.153                                                                              0.160                                                                              0.155                                                                              0.174                                      Aged K-Factor, 1 Week                                                                      0.189                                                                              0.188                                                                              0.207                                                                              0.194                                                                              0.204                                                                              0.198                                                                              0.200                                      __________________________________________________________________________      Voranol 370 is polyol; Hyd. No. 355-385; marketed by Dow.                      Fluorocarbon 11SBA is stabilized fluorochloromethane; marketed by Allied.

EXAMPLE 17

A reaction injection molding formulation for the production of automotive bumper fascia was chosen for comparing the behavior of the compounds of this invention to the commercial catalyst dibutyltin dilaurate. The composition of the formulation used was as follows:

    ______________________________________                                         Formulation 5                                                                  Component       pbw                                                            ______________________________________                                         .sup.(13) Pluracol 380                                                                         100.0                                                          1,4-butanediol  23.0                                                           Catalyst        0.025                                                          .sup.(14) Mondur CD                                                                            79.5                                                           ______________________________________                                          .sup.(13) Pluracol 380  high mol. wt. triol; marketed by BASF Wyandotte        .sup.(14) Mondur CD  carbodiimide containing isocyanate; marketed by Moba                                                                               

Plots of gel time and tack free time versus temperature in the range 70° to 100° F. clearly show that the catalyst of the invention activated by heat more than standard catalyst T-12, a feature that is very desirable in that it allows time to fill the mold with rapid cure and thus a shorter cycle.

EXAMPLE 18

The desirable delayed action behavior of the compounds of the present invention was demonstrated in yet another formulation. This formulation is typical of those used in making urethane shoe soles. Its composition is as follows:

    ______________________________________                                         Component        pbw                                                           ______________________________________                                         .sup.(15) Voranol 4701                                                                          100.0                                                         1,4-butanediol   10.0                                                          .sup.(16) Freon R-11B DuPont                                                                    7.0                                                           .sup.(17) L-5303 1.0                                                           Catalyst         as shown in table                                             .sup.(18) Isonate 181                                                                           51.0                                                          ______________________________________                                          .sup.(15) Voranol 4701 is Dow polyol; Hyd. No. 31.7-36.6 triol.                .sup.(16) Freon R11B is DuPont's chlorofluoromethane.                          .sup.(17) L5303 is silicone surfactant; marketed by Union Carbide.             .sup.(18) Isonate 181 is aromatic isocyanate; marketed by Upjohn. % NCO        content by wt. = 22.8; eq. wt. 184.                                      

The premix including the catalyst was mixed with the isocyanate for 10 seconds, then poured into a preheated aluminum maze mold of 12"×12"×1/4". The temperature of the mold surface at the time the reaction mixture was poured was 150° F. The flow of material inside the mold was followed by recording the time when it oozes out of the four vent holes at each corner of the mold. Demold time was varied and Shore A hardness was recorded immediately after demolding. Table IX summarizes data obtained.

                  TABLE IX                                                         ______________________________________                                         Evaluation of Experimental Amino Tin Catalysts                                 vs. UL-1 (dibutyltin dilaurate)                                                Temperature of Resin 86-87° F.                                                       Time Material Extrudes                                                                         De-                                               Concent.     from Vent Holes, secs                                                                          mold                                                      php      1st    2nd  3rd  4th  Time, Shore                             Catalyst                                                                               polyol   VH     VH   VH   VH   mins  A                                 ______________________________________                                         Dibutyltin                                                                     dilaurate                                                                              0.03     43     44   48         3*   35                                        0.03     43     45   47         5*   39                                Catalyst of                                                                    Example 6                                                                              0.03     29     31   33   36   5     38                                Catalyst of                                                                    Example 12                                                                             0.03     28     30   33   35   7     45                                Catalyst of                                                                    Example 7                                                                              0.03     31     32   35   37   3     34                                ______________________________________                                          *Mold was never completely filled and thus material did not flow far           enough to reach the 4th venting hole.                                    

It is clear from the above table that compounds of the present invention provide for better flow (shorter time to fill mold) than commercial catalyst dibutyltin dilaurate.

EXAMPLE 19

The versatility of the catalysts of the present invention was ascertained by evaluating them in a variety of flexible foams. The formulations chosen were those of water-Freon and water-methylene chloride blown systems. The composition of these formulations and comparative reactivity data are shown in Tables X and XI.

It is clear from Tables X and XI that the compounds of the present invention are superior in activity to standard catalyst such as T-12. They also provide for longer cream time and/or shorter hard gel times than the combination of T-9-amine catalysts.

                                      TABLE X                                      __________________________________________________________________________     Freon-Water Blown Formulation                                                                  Component  pbw                                                              (19)                                                                              Voranol 3010                                                                             100.0                                                             (20)                                                                              Genetron 11SBA                                                                           7.0                                                                  Water     3.6                                                               (21)                                                                              L-6202    1.0                                                                  Catalyst  As Shown                                                          (22)                                                                              Mondur T-80                                                                              47.0                                                                 Premix Temp.                                                                             83° F.                                                  Concentration, pph Polyol                                            __________________________________________________________________________     Catalyst                                                                       T-9/DOP (1/3)                                                                            1.0               1.0                                                (23) DABCO TL                                                                            0.2               0.2                                                Example 10    0.8                                                              Example 7          1.0 1.1                                                     Example 12                      0.4                                            Reactivity                                                                     B.O.R., Secs.                                                                            11  16   17  17   11  12                                             Rise, Secs.                                                                              110 100  100 100  105 100                                            Hard Gel, Secs.                                                                          115 92   110 100  105 95                                             Rise Height, Inches                                                                      81/2         91/4     91/2                                           Foam Rating                                                                              Good                                                                               Good Good                                                                               Good Good                                                                               Good                                                     Open                                                                               Open Open                                                                               Open Open                                                                               Open                                                     Cells                                                                              Cells                                                                               Cells                                                                              Cells                                                                               Cells                                                                              Cells                                          __________________________________________________________________________      (19) Voranol 3010 is high molecular wt. triol; marketed by Dow Chemical        Corporation.                                                                   (20) Genetron 11SBA is Allied Chemical chlorofluoromethane.                    (21) L6202 is Union Carbide Corporation silicone surfactant.                   (22) Mondur T80 is an aromatic isocyanate; marketed by Mobay Chemical.         (23) DABCO TL is a tertiary amine catalyst; marketed by Air Products and       Chemicals, Inc.                                                          

                                      TABLE XI                                     __________________________________________________________________________     Methylene Chloride-Water Blown Formulation                                                    Component    pbw                                                              Voranol 3010 00.0                                                              Methylene Chloride                                                                          8.0                                                               Water        3.6                                                               Silicone L-6202                                                                             1.5                                                               Catalyst     As Shown                                                          Mondur T-80  41.6                                                              Premix Temp. 72° F., 80° F.                                  Concentration, pph Polyol                                            __________________________________________________________________________     Catalyst                                                                       50% T-9 in DOP                                                                           0.8 *                   *                                            DABCO TL  0.4 0.1 0.1 0.2 0.2 0.1 0.1                                          T-12          0.3                                                              50% (Example 10)  1.6 0.8                                                      50% (Example 7)           0.6     0.6                                          Reactivity                                                                     B.O.R., Secs.                                                                            13  22  17  17  19  22  19                                           Rise, Secs.                                                                              95  120 110 95  95  110 90                                           Hard Gel, Secs.                                                                          105 145 100 100 100 120 105                                          Rise Height, Inches                                                                      81/2                                                                               83/4                                                                               91/2                                                                               81/2                                                                               81/2                                                                               83/4                                                                               83/4                                         Foam Rating                                                                              Good                                                                               Good                                                                               Good                                                                               Good                                                                               Good                                                                               Good                                                                               Good                                                   Open    Open                                                                               Open                                                                               Open                                                                               Open                                                                               Open                                                   Cells   Cells                                                                              Cells                                                                              Cells                                                                              Cells                                                                              Cells                                        __________________________________________________________________________      * Premix temp. = 78° F.                                            

What is claimed is:
 1. Compounds corresponding to either of the formulae: ##STR21## wherein R₁ and R₂ are independently H, alkyl of 1 to 20 carbon atoms; hydroxyalkyl of 2 to 20 carbon atoms; or R₁ and R₂ together form a heterocyclic ring of 5 or 6 atoms; ##STR22## in which n equals zero or one and R₆ is hydrogen or an alkyl or an alkyl hydrocarbyl group of up to 20 carbon atoms;A and B are carbon atoms linked by a single or double bond or together comprise part of a six membered ring from the group consisting of cyclohexane, cyclohexene and benzene; R₄ and R₅ are independently alkyl groups of 1 to 20 carbon atoms, phenyl or cycloalkyl groups of 6 to 20 carbon atoms.
 2. Compounds of the formula: ##STR23## in which each R is a substituent from the group consisting of methyl and ethyl.
 3. Compound of the formula: ##STR24##
 4. Compound of the formula: ##STR25##
 5. Compound of the formula: ##STR26##
 6. Compound of the formula: ##STR27## 